Kneader polymerization process for olefins



Fehs, 1948.v f MUM/mum 2,435,229

KNEADER POLYMERIZ-ATION PROCESS FOR OLEFINS Filed June 23, 1944 8 Sheets-Sheet`1 mabew D; 772cm Jn nvenbor- Qbnorneq Feb. 3, 1948. M. D. MANN, JR

KNEADER POLYMERIZATION PROCESS FOR OLEFINS 8 Sheets-Sheet 2 Filed June 2z, 1944 Fia- 2,

M. D. MANN, JR

KNEADER POLYMERIZATION PROCESS FOR OLEFINS Feb. 3, 1948;

Filed June 23, 1944 8 Sheets-Sheet 3 23a@ uwen@ avanzano uz... 05550. 53.5 uruuu baal du mm mpv (1bn orner* M. D. MANN, JR

Filed June 2:5 1944 8 Sheets-Sheet 4 amnwrm mtfzew D. 772mm J2.'

Unverzbor u. e n n o L L Q Feb. 3, 1948.

KNEADER POLYMERIZ'ATION PROCESS FOR oLEFINs Feb. 3, 1948. M. D. MANN, JR 2,435,229

` KNEADER POLYMERIZATION PROCESS FOR OLEFINS Filed June 23. 1944 a sheets-sheet 5 FIG. 4

mcliibew Dfmcnn Jr. :nvntor Feb. 3, 1948. M. D. MANN, JR V 2,4355229 KNEADER POLYMERIZATION PROCESS FOR OLEFINS Filed June 2s, 1944 a sheets-sheet s Fish-5,

mall/:em D. mann Jn [inventor bq 7%? Cltmorneq Feb. 3, 1948. M. D. MANN, JR 2,435,229

KNEADER POLYMERIZATION PROCESS FOR OLEFIS Fled June 23, 1944 8 Sheets-Sheet 8 similar substances are also useful.

Patented Feb. 3, 1948 Matthew D. Mann, Jr.; Roselle, N. J., asslgnor, by mcsne assignments, to Jasco, Incorporated, a. corporation of Louisiana Application June 2a, 1944, serai Nb. 541,715

This invention relates to processes for the low 1l- Claims. (Cl. 260-93) temperature polymerization of olenic substances; relates particularly to continuous low temperature polymerization processes in which portions of the materials are recycled; and relates especially to methods for separating the Ipolymer from the recycle stream without loss of recycle material; and further relates to methods for the reduction of fire and industrial poisoning hazard otherwise inherent in unconflned Various low boiling liquids such asliquid propane,

liquid ethylene, or liquid ethane are preferably used as refrigerants; carbon dioxide, either solid or liquid, in solution in the hydrocarbon material is likewise useful; and various diluents such as propyl, ethyl or methyl chloride, and other The polymerization may be conducted in batch operation, but great difficulty is encountered in recovering the various refrigerante, diluents and unpolymerized reactants, since most of them are gases at room temperature, and evenat temperatures only slightly above the reaction temperature.

These characteristics of the substances making up the reaction mixture, together with the very great stickiness and solid character of the polymeric product, makes it exceedingly diicult to separate the polymer from'the reaction mixture without the loss of undesirablelarge portions of the gaseous diluent-refrigerant and the development of a serious re hazard and .indus-- when substantial quantities of gaseous hydromerization process for the separation and recovery of the solid polymer and the volatilized gaseous portions of the reactant mixture, substantially without loss of any of the volatilized diluent-refrigerant or reactant substances; thereby avoiding the loss of' valuable materials and, in addition, avoiding the development of fire or industrial poisoning hazard.

The process is particularly advantageous for the preparation of copolymers of an isoolefln with a polyolefln, isobutylene being the preferred isoolen; 2, methyl butene-l and 2, methyl pentene-l likewiseebeing useable under some circumstances. The polyolefln may be isoprene, piperylene, dimethyl butadiene and, in fact, substantially any of the polyoleflns having 2 or morel double linkages, whether conjugated or non-conjugated with carbon numbers from 5 to 12 or 14 inclusive per molecule being satisfactorily useable. Butadiene is also useable under certain circumstances but is not a preferred component, since it is diicult to get a fully satisfactory polymer when the yield is carried to the extent required for satisfactory operation of the process.

Broadly, the process of the invention consists vof the polymerization of the olenic material in a kneader under the influence of kneader blades;

vthe solid polymer being passed through a series of kneaders and processed in each one, and then worked during an extrusion step to complete the `separation of polymer and diluent-refrigerant carbons are freed in a room. Such hydrocarbons yield combustible or explosive mixtures with air, when more than a very small percentage of the `hydrocarbons is present, and at concentrations below the explosive or combustible range, they or unpolymerized olefin while separating the polymer from gaseous material and discharging both from the reactor system.

The reactor vessel may be a container adjacent to and associated with the extruder member, the reactor vessel preferably containing kneaderblades for transferring the solid polymer to thelextruder; or the reactor vessel may consist of a plurality of members arranged in cascade, each with kneader blades for transferring the polymer from one chamber to the next.

. The reactor system may be jacketed with a coolant to maintain the desired low reaction temperature within the range between 10 C. and C., preferably within the range between 50l C. and 165 C., with the solid polymer being consolidated and ejected by the extruder polymerization is conducted in an adjacent, associated reaction vessel and the solid polymer' is transferrediromthe reaction vessel to the eX- truder, the extruder is preferably lequipped with a heating means such as a. steam jacket, in order to volatilize from. the solid polymer, any residual Alternatively, and preferably, if the.

easier extrusion. When the reaction is conducted in an adjacent, cooperating reaction chamber, either in a single reaction chamber, or in a pluralityof reaction chambers, they are desirably heat insulated, and may conveniently be jacketed with coolant, as previously described.

The extruder and the reaction vessels, if Such are used, are preferably tightly closed with solid covers', and are provided with supply pipelines` for the delivery of the various component parts of the reaction mixture to the reactor, and are further provided with discharge lines for lthe transfer of volatlli'zed portions of the mixture to recycle equipment in which the mixed gases are fractionated, cooled and condensed for reuse as` portions of a further quantity of reaction mixture.

Thus an object of the invention is to polymerize an olenic material continuously, while continuously removing from the polymerization container the solid polymer, and recovering substantially all of the volatilized reactionmixture components for reuse and recycling, while avoiding the development of re hazard or industrial poisoning hazard, `by the association with the reaction container of an ext-ruder mechanism which eects only the solid polymer from the reaction mixture. Another obiect is to copolymerize an isoolen and a polyolen by the application thereto oi a catalyst under the iniluence of kneader blades. Other objects and details of the invention will be apparent-from the following description when read invconnection with the accompanying drawings; wherein Fig. 1 is a side view in elevation of an embodiment of the polymerization reactor of the invention;

Fig. 2 is a side view in sectional elevation of the embodiment of Fig. 1;

Figs. 3 and 3A together show the iiow of materials for the polymerization reaction and the recovery of the volatilized materials and the solid polymer;

Fig 4 is an end view, partly in section of the embodiment of Fig. 1; Y

Fig. 5 is a top view of the embodiment of Fig. 1. Fig. 6 is a sectional view in vertical elevation of the catalyst dissolving member;

Fig. 7 is a side view in vertical section of an alternative embodiment of Fig. 1 showing means in the form of hydraulically operated top closure members for clearing the kneader members of excess polymer when diilicuity is encountered in transferring the polymer from one kneader to another.

'I'his application is a continuation-impart of my co-pending application Serial No. 368,967,

led December 7, 1940, for polymerization apparatus; which in turn is a continuation-impart of my application Serial No. 684,313, filed August 12, 1933, now Patent Number 2,229,661, issued January 28, 1941, and copending with Serial No. 368,967; and of my application Serial No. 249,682,

` filed January 7, 1939, now Patent Number 2,360,-

. r 4 moval of the vaporized constituents, and the extruder outlet for the discharge of the solid poly- "mer, The reaction mix components are preferably delivered through pipes to the iirst, uppermost lmeader, and the polymerization initiated therein. The polymerization reaction liberates relatively very large quantities of heat, which quantities of heat are absorbed by the diluent-re- Irigerant, usually liquid ethane or liquid ethylene present in the reaction mixture. The reaction is rapid and the heat of reaction volatilizes a major portion of the diluent-refrigerant to praetically all of the diluent-reirgerant.

During the reaction, with isobutylene as the reactant, practically all of the isobutylene is converted into the solid polymer which is transferred by the kneader blades into the next adjacent kneader device in the cascade sequence. In this second lmeader, and to some extent in the rst kneader as well, the solid polymer is cut and broken into relatively small granules or crumbs, and residual quantities of the diluent-refrigerant and any unpolymerized reactants are largely driven oi from the solid polymer. The breaking up and vdegassing may be continued in a third lmeader to which the solid polymer is transferred by the blades of the second kneader, and at the conclusion of treatment in the third kneader, the material is delivered linto a heated extruder, in which substantially all of the diluent-refrigerant, catalyst, and any other volatile materials are volatilized from the solid polymer, under a plenum or low gas pressure, and the solid polymer is discharged through the extruder nozzle as a continuous stream which seals the discharge from the reactors against leakage of volatilized gas; thereby avoiding the loss and wastage of valuable materials;vavoiding the development of a re hazard from admixture of these hydrocarbon gases with air, and avoiding the de.. velopment of an industrial poisoning hazard, since most of these substances have anaesthetic and poisonous properties; and, in addition, permining of the return of the velatuized gaseous fer of the polymer from kneader to kneader and parts of isobutylene yields a satisfactory polymer, since the proportion of diolen which interpolymerizes does not depart very widely from the proportions in which it is present. With butadiene, however, it is found that the butadiene does not interpolymerize in the proportion in which it is present, but that a relatively very large excess is required to cause the interpolymerization of the desired relatively small amount, and accordingly, as the isobutylene is interpolymerized, it is used up, leaving in the reactor a mixture which may contain an undue proportion of butadiene with respect to the proportion of isobutylene, from which a copolymer undesirably aimons high in butadiene is obtained. 'nie resulting' co- 1200 to 4600 pounds at .break with an elongation at break ranging from 400% to 1200%, together with phenomenally high abrasion resistance, flexure resistance. ozone resistance and similar properties, much superior to those of natural rub-.

ber.

Referring to the figures, a base plate member I is provided, upon which'the frame members 2 of the reactors are mounted.' As is particularly well shown in Fig. 2, the frame members 2 form the sides, ends and bottoms of a series of kneadermixers in which there are located S" type kneading and mixing blades 3. -These blades 3 operate in pairs, as shown, and each pair of blades has its own frame and housing as is shown in the drawings. 'I'he respective housings are covered and closed by covers 4, 5 and 6, respectively, equipped with sight glasses or inspectionwindows 1, 8 and 9. Each housing, except the last, may if desired, be equippedwith a discharge opening controlled by an adjustable gate II, which is moved up and down by a threaded rod I2 controlled by `a hand wheel and nut assembly I4; this gate vstructure may usually be -omitted however.

Under some operating conditions, especially when the polymer is unusually sticky, some dimculty may be encountered in transferring it from kneader to kneader. This difilculty is readily overcome by the use of the ram structures shown in Fig. 7. The plate actuated by `the ram is brought down practically against the top of the kneader blades. The reaction between the kneader bladesand the ram plate forces the polymer out of the kneader quite rapidly into the next kneader, whereupon the ram plate in the second kneader may be brought down to force the poly-`- mer into the third kneader, the third ram then being brought down to force the polymer into the 6 power source may conveniently be individual electric motors (not'shown). The gears 22 are desirably shielded and protected by a gear case 24. The respective extruderworms are driven through gears 25 bypower from a convenient source supplied through the shaft 2 6, The respective shafts are desirably equipped with eilicient packing glands 21 as shownin Fig, 5 in order to prevent leakage of the polymerization mixextruder by which it is forced out of the reactor' rbrought to -bear upon the polymer and it may, by

this procedure, be transferred through the desired sequence of kneadlng stages and discharged, under almost any conditions of stickiness, stiffness or toughness, thereby avoiding all question of clogging of the kneader, which is an exceedingly diillcult problem with all other types of reactors.

The last'kneader of the cascade series has a' discharge opening -beneath 'the second of the kneader blades 3 which leads to an extruder device IS mounted' upon legs I6 -and having extruder screws I1 terminating at a discharge outlet I8 through 'which the solid polymer is discharged.` The extruder I5 has a steam jacket I0 by which the polymer discharged from the last blade 3` onto the extruderscrews I1 is rapidly warmed up Aand any residual olenic raw ma# teria] or'diluent-refrigerant is rapidly volatiliged and sent backward in countercurrent direction through the successive kneader devices toa gas discharge port 2| which leads to therecovery and recycling processes.

The respective pairs of kneader blades 3 are driven'in opposite directions rby gear members 22, which preferably drive the respective blades 3 of each pair at a 2 to 1 speed ratio. Each pair of blades` is preferably driven by a suitable power source applied to the respective shafts 23'.-l This ture, as well as vaporized portions of the reactant mix resulting from the high heat of reaction ot'the polymerization from the kneader chambers.

The various components of thepolymerization mixture are preferably delivered to the first of the kneaders through delivery pipe lines 28 which are desirably extended inside of the rst kneader chamber to a point as close to the rst ofthe kneader blades 3 as possible. The ends of the respective pipes ZB-are'preferably brought close together, in order to discharge the two streams of. reactants and catalyst into the same neighborhood in order to promote as rapid mixing as possible. v

The cascade kneader system may be equipped with a single gas outlet 2l as shown, or each of.

the successive kneader sets may be equipped with separate gas outlets 2|.

Referring to Figs. 3 and 3A, the kneader system K, shown at the right of Fig. 3A with the gas outlet pipes 2|, and the supply pipes 28, is connected to a 'source of boron triuoride in the form of cylinders of the liquefied gas 3I which are connected through a pipe and valve system 32 toone of the supply pipes 28, which is 'also connected by a supply pipev 33`to a storage reservoir 34 containing ay supply of liquid diluentrefrigerant, preferably liquid ethylene. A second of the supply pipes v28 is connected by way oi supply pipe 35 and cooler 36 to storage drums 31 containing liquid isobutylene.

A by-pass supply pipe line 38 with control valve as indicatedleads from the pipe 33 to the pipe 35 for the delivery of liquid diluent-refrigerant to mix with the liquid isobutylene preparatory to delivery into the kneader system K. The gas outklet pipes 2I are connected to atransfer pipe line 39 which leads, as shown inFig. 3, to a scrubber I drum 4I for the removalof any liquid constituents. From the drum 4ly a second pipe line 42 lleads to a scrubber device 43 which consists of a closed container charged with calcium oxide whichserves to remove from the effluent any residual traces of boron triuoride. From this drum 43, the ethylene or ethane vaporisv discharged through pipe lines 44and 45 to storage or surge drums 4B. From the drums 46 a pipe line 41 leads the effluent, which is largely gaseous ethylene or ethane free from boron tr'ifiuoride but containing small quantities of isobutylene, and on occasion small quantities of isobutylene dimer and trimer (and if diolefins are-used in the reaction mixture, may contain small quantities of the diolens), to a compressor system48 in which the gas is compressed and cooled preparatory to liquefaction. TheV compressed gas is passed-through purifying. towers 49 containing solid calcium chloride for` the removal of all traces of moisture. -to a fractionating column 5I.

rlgeration together with a' circulating pump I3 and a storage drinn I. The relatively pm'e ethylene or ethane loaves the column 5I by way f of a pipe line 55, which is associated with a series of storage containers 5i. A second pipe line 51 is connected to the pipe line 55 through the pipe manifold shown, and is further connected through a control valve to the pump 53, the condenser 52 and the storage tank 5I. A pipe line 5l leaves from the storage drum 5I to an auxillary flow drum' 59 and a delivery pipe line 6I to the lower pipe manifold system shown associated with the storage drums Si. Liquid ethylene or ethane condensed under the operating pressure in the condenser 52 is thereby delivered to a storage drum 62 from which a portion is removed by the pump 63 and sent by way ot pipe line .64 to the top of the fractionating column 5i to provide the necessary liquid redux. A steam -coil i5 vaporizes a portion oi' the reflux at the bottom of the fractionating tower 5|, and a portion of the heavy ends is discharged through an outlet pipe 66 from which it may be sent to the waste gas lines. Another portion of the ethylene or ethane, including any traces of hydrogen, or other more diilicultly condensable gases may be discharged through the pipe line 61 to -a burning line or to the waste gas line as desired.

A supply of impure ethylene or ethane (from the refinery fractionating column) in the form of a C2 cut is received through pipe line 68, passed through a. water scrubberi, through a vapor extractor il through a knock-out drum 12 to drier cylinders i3 which are lled with solid calcium chloride to remove all traces oi' moisture. From the drier drum 13 the raw4 ethylene or ethane is passed through a pipe line 'M to the tower 15. A substantial portion of cold liquid puriiied ethylene or ethane is delivered from the storage drum 62 by way of the supply pipe line 16 to the top of the tower 15 to form a. reux. A steam coil 'l1 is provided in the bottom of the tower 'I5 to vaporize a portion of the reflux. By this arrangement, substantially pure ethylene (with small quantities only oi ethane) or ethane is delivered through the pipe line 'I8 to the pipe line 19 leading to the pipe line 45 and the ethylene storage drums 46. 'I'he heavy ends from the tower are delivered to a flash drum'l containing a. steam coll which converts the liquid material into gas at approximately room temperature, for return to the reiinery fuel lines (to avoid the development of low temperatures which would freeze up the lines). Simultaneously, a major portion of the liquid ethylene or ethane is delivered from the storage drum $2 through a pipe line 82 to the storage drum 34 for use in the polymerization reaction.

The nearly pure isobutylene is delivered from the refinery through pipe line 83 to the drum 84 of a fractionating column 85. The nearly pure isobutylene is received from the renery at approximately atmospheric temperature under a pressure of to 50 pounds, depending on the atmospheric temperature. A portion of the isobutylene is volatilized in the drum 84 and rises through the fractionating column 85 to the pipe line 86 by which it is conducted to condenser 81 where it is condensed and delivered 8 iromthedrinnltostorageortoailash drumorto other convenient means for disposal.

. Another portion of the liquid isobutylene is taken iromthedrmnllthrcughpipeline tothe storage drums 91 in which the liquid isobutylene is stored, and from which it is delivered from the pipe 35 to the polymerization reactor K as above described.

The above outlined procedure suggests the use of liquid hydrocarbons as reirigerants. Carbon dioxide is, however, en equally satisfactory refrigerant.l Liquid carbon dioxide at temperatures from '10 to 78 C. shows a very high solubility in the liquid hydrocarbons such as butano, propane, and the like, and the cooling may be ob tained by delivering to the reactor a solution oi' carbon dioxide in propane or butane or even in pentane. The temperature resulting from this mixture is within a. very few degrees oi the temperature of solid carbon dioxide at 78 C., and temperatures as low as 75 to 77 C. are readily obtained by the use of solutions of liquid carbon dioxide in propane.

Example 1 In the operation oi the invention, liquid ethylene is withdrawn from the tank 34 through the pipes 33 and 28 into the reactor and allowed to volatilize therein until the entire reactor structure is cooled down to the desired low reaction temperature. During this cooling operation, the yolatilized gas is discharged through the pipe 2| to the storage drum 4| and through the scrubber l3 to the drums 46. When the desired low temperature is reached, a further portion of the liquid ethylene is passed through the pipe 38 into the second pipe 28, and thereafter 4liquid isobutylene or a mixture of isobutylene with one or more of the above-indicated polyolens from the drums 3l is passed through the pipe 35 and the cooler 3B to the second pipe 28 and discharged into the reactor 2 adjacent the iirst of the kneader blades 3. Simultaneously with the delivery of the isobutylene-ethylene mixture to the reactor, boron triuoride is delivered through the line 32 and mixed with and dissolved in the liquid ethylene from pipe 33. By this procedure delivered to the reactor; preferably through a supply pipe leading to the bottom of the rst kneader in the cascade, 'This is especially effective when isobutylene is being polymerized alone, but it is also satisfactory with mixed olefins, especially mixtures of isobutylene with 2,3 dimethyl butadiene 1,4. This dioleiin is particularly advantageous for the procedure here described, because of the fact that it copolymerizes under the influence of boron trfiuoride in very closely the exact proportion in which it is present in the mixture, and the polymerization may conf veniently be carried to yields ranging from to 95% of the olenic material fed: whether dissolved boron trliluoride is used, or gaseous boron triuoride is used The resulting copolymer cures very readily to a very high-grade substitute for natural rubber. f

When other polyolens are used, it is desirab that either dissolved boron triuoride in ethylene or ethane or even propane be used or that aluminum chloride in solution in a low-freezing, non-complexforming solvent such as ethyl or been removed from the polymer.

4 y 9 methyl chloride or carbon disulfide be used, since a, more nearly proportional copolymerization is obtained, a higher molecularweight is obtained, and a higher yield is obtained, all of these factors resulting in a, more'satisfactory operation of the process.

The polymerizationv reaction is a very rapid one, liberating a very substantial amount of heat yof reaction, and thereby volatilizing the diluentrefrigerant at a, relatively high rateof speed.

' i The reaction is complete in a time interval varying from a few seconds to a very small number of minutesand accordingly, while a pool of the reactants is formed by the streamsof material in the bottom of the reaction chamber, the reaction is so rapid that the contents of the reaction chamber (the first kneader in the above outlined embodiments) consists mainly of the solid polymer with only very small amounts to negligible amounts of liquid remaining, and small amounts of liquid adhering to, and occluded in, the solid polymer. The kneader blades 3 in the first kneader throw the solid polymer into the second kneader where a small amount of additional polymerization may occur, but in which the main procedure is the pulverizing and breaking up of the mass of polymer into moderately small granules and the freeing of the polymer from most of the occluded and adhering liquid, the liquid being -volatilized and discharged from the kneaders.

The action of the kneader blades throws the solid polymer into the third kneader, from which it passes downward to the extruder screw I1.

At this stage, the polymerization is complete, and nearly all of the volatilizable material has The extruder screws l1 may be provided with a steam jacket I9 and the solid polymer, in contact 'with the screws l1, is rapidly brought up to a much higher' temperature,.at which it is greatly softened,land

all residual tracesy of volatilizable matter are rapidly driven out.

The solid polymer is caught by the extruder i screws I1 and carried toward the discharge end of the extruder. Thev extruder screws run at a good speed, and the solid polymer is passed rapidly toward thedischarge end of the extruder. As long as a substantial quantity of polymer is in contact with the extruder screws, it is pushed to. and through, the outlet. Simultaneously, the

-solid polymer is compacted at the discharge end into a solid mass iilling the entire discharge nozzle, with al1 of the gaseous and gasied material derived from unpolymerized raw material and from the diluent-refrigerant or other sources, squeezed out of the solid. Under these circumstances, an impervious plug of solid, but somewhat plastic, polymer fills the discharge outlet of the kneader and prevents the loss or leakageof any gaseous material, thereby sealing the discharge end ofthe system against the loss of valuable materials and sealing the system against emergence of vapors which could produce either la re hazard or an industrial poison hazard, yet permitting the simple and easy discharge of solid polymer product as rapidly as it is produced, after aseries of purication steps to removesubstantially all of the undesired and vundesirable volatile material. c

Thus the polymerization -occurs very rapidlyin the rst kneader, and the reaction is vso rapid that little or no pool of rea-etant materialsv occurs in the kneader, but the contents ofthe` kneaderare mainly solid polymer with asmaller quantity of actively polymerizing liquid reactants.

' discharged from-the ilrstkneader, the reaction mixtures.

" variation. A lpreferred form per cent by weight of the amount of kisobuty Ais almost entirely completeand nonly asrnall amount of polymerizatlo lrifd iii"nefgiig'giily amounts of polymerizatio second kneader. f The emergent gases consist mainly'fof gase smaller quantities offg smaller quantities of .bor I in some instances contain som vti' es butylene dimer or trim "n efiiuent is passed to thk the calcium oxide `sci-ulileril o where any traces of dimer 'or trime trifluoride are removed, leaving subst ethylene with minor trace l ofisobu l ethylene is compresserhpurY jdjbyfvf A titi as shown in Figs. 3 and the storage drum 34 forrl The composition 'of the." u y viously mentioned, is sbj` l the simple polyisobutylenec Y mately one part by weigh .ofliqv` df with two and one-half ,to'ftlir of liquid ethylene, together by weight to 0.001 partwofbor catalyst. That is, the amount'ofi'dilue erant required to absorb theheatgofpol y l non is from two and one-hair otnreftimesfthc amount of isobutymne present', ,nd the amount; of catalyst required ranges fronr'ifn A* to one per cent by weight crjthe'airicunt 61 butylene present. I'

`When liquid ethane is used, approximately tlie,` same proportions of reactants arek satisfactory",- When liquid propane is used,'.approximate1ythe` same proportions of reactants are likewise satis-,f factory.

In the above paragraphs, itl'has been suggested thata simple mixture containing isobutylene only as a reactant mixture may beusedly ',It is possible, n

however, to use a vconsider/able .riliinbc'r,of` otherN For instance, the 'isobutylefne'fmay`v l be replaced by methyl ethyl ethyleneas thefreactant, and more than one olefinic'substancemay,I be present as a reactant. Especiallyftheremay be used diolenic constituents sueltas -biitadiene,l'` isoprene, cyclopentadiene and dimethylbutadiene," f as well as various otherdiolenic substlances."'`

- Likewise, other catalysts thanboronuoride may be used, such as, for instance, aluminum chloride, dissolved in a simpleA solution inl a'low frecezingv solvent which does not forma complex with the; aluminum chloride, such as'ethyl or methyl ohioride or carbon dlsulde. 'i

In preparing the respective components ofthe, reaction mixture, the liquid isobutylenefand thev liquid ethylene may simply be mixed, `pre'fei'jably,.-y

at the temperature set by the boilingpointunden atmospheric vpressure of the ethylenel since the isobutylene (and any other added olenic mate riais) are readily soluble in the ethylene Whilih serves as the diluent-refrigerant. In preparingl i the solution of catalyst, the gaseous boron trifluoride may, if desired, be dissolved in a portion offthe liquid ethylene by a device as shownin Ilig,y 6, although-:this is not necessary, nor always-convenient. This device may conveniently 'consistof' -a vessel or container 636 to whichY the ethylene supply pipe'33 is connected, and withinwhich a` secondary member 646 is positioned and-connected at the top to the catalyst solution outlet 11 pipe 28. The boron trifluoride pipe 32 is connected to a bubbler head III within the member 646. The liquid ethylene nowlng from the pipe made up in a diluent only, with the refrigerant kept separate.

Alternatively. the respective components of the reaction mixture may be delivered separately to the reactor, the isoolefln being delivered through one supply line, the diluent-reirigerant through another and the catalyst through a third. Alternately, gaseous boron triiluoride may be delivered to the reactants in the reactor through a supply pipe G6 entering the bottom of the reactor as shown in Fig. 1. This form is satisfactory, il.' a suiiiciently rapid stirring oragitation of the reactants is available, but in the event that the reaction mixture is only slightly stirred, this is determined to yield results shown the following table:

Modulos Tensile Per cent sm om @rzl stli'fh Elongation 137' a, no 925 io n. bm an' cme sos soo p a mi s 163 1opts.black@eo'mre 4.060 ses i m 4,040 su sopnbimkgso'm gg? 77g so pa buck e on' cum 5 m 51 321m 615 less satisfactory than the other methods above described.

The above described embodiment utilizes a series .of reactors arranged in cascade, but it is not necessary that the three: be used. Equally satisfactory results, especially when the highest possible molecular weightpolymer is not necessary, are obtained by the use oi.' only two kneader members in cascade. In this embodiment, the uppermost pair of blades and container are omitted, and the cover with its sight glasses 1 and inlet pipes 28 is placed over the iirst one of the two kneaders.

Example 2 A representative kneader polymerization of mixed oleiins was conducted on a feed stock prepared from 98.55 parts by weight of isobutylene of 99% purity and 1.45 parts by weight of isoprene of 96% purity. To this was added 400 parts by weight of liquid ethylene. The kneader reactor was cooled by liquid ethylene in a manner similar to that above pointed out and when a temperature of approximately 95 'C. was reached, the pure ethylene was discontinued and the feed, prepared as above described, was delivered to the kneader. Simultaneously, approximately 10 parts by weight per 500 of olenic material of a catalyst consisting of a 0.57% solution of aluminum dibromo chloride in methyl chloride `was delivered to the kneader reactor. The polymerization occurred very rapidly as before. A yield of 76.7% of the amount of isobutylene and isoprene was obtained and the polymer had a molecular weight within the range of 24,000 to 120,000 (as determined by the Staudinger viscosity method) Samples of the polymer were compounded according to the following recipe:

These samples were cured at 307 F. for 30 and 60 minutes; test samples were cut from the cured material and the tensile strength and elongation mms3 A similar feed stock to that in Example 2 was prepared 'using piperylene as the polyolen; 97.5 parts by weight of isobutyiene of 99% purity being mixed with 2 5 parts by weight of piperylene of 96% purity. To this mixture there was then added approximately 400 parts by weight of liquid ethylene and the material was stored. The reactor was cooled, as above described, and when the desired low temperature had been reached, the feed mixture containing the oleflns was sent to the kneader. Simultaneously, a catalyst, consisting of aluminum chloride in solution in ethyl chloride in a concentration of approximately 0.5% was added at a rate corresponding to approximately 11/2% of the rate oi' delivery of the olenic feed material. The catalyst was added in the form of a line spray onto the surface of the feed in the kneader; the kneader blades being continued in operation, submerged in the liquid feed. The reaction began promptly and the polymerization continued until most of the contents of the kneader consisted of solid polymer. Simultaneously, continuing quantities of feed and catalyst were added to the kneader to keep the kneader full of solid polymer and reaction mixture and the procedure was continued as before.

The resulting polymer was compounded according to the recipe of Example 2, and evaluated and found to be readily curable with sulfur, especially in the' presence of tetramethyl thiuram disulfide to yield a cured polymer having a. tensile strength of approximately 3000 pounds per square inch and an elongation at break of approximate- 1y 1150%. l

Example 4 An olefinic mixture was prepared consisting of approximately 97 parts by weight of isobutylene oi' approximately 99% purity and 3 parts by weight of isoprene of approximately 96% purity. To this mixture there was then added approximately 400 parts by weight of liquid ethane; and the prepared mixture was stored as above indicated. The kneader polymerizer was then cooled to approximately 88 C. by the delivery thereto of a substantial quantity of liquid ethane. When the polymerizer was adequately cooled, the supply of liquid ethane was discontinued and the feed, as above prepared. was substituted. When the kneader was nearly full of oleiinic feed, a supply of catalyst consisting of a solution of-aluminum chloro-bromide in ethane was delivered under high pressure in the form of a very Ene jet into the olenic material while the kneader blades were in normal rotation; The reaction began 13 promptly to yield the desired polymer. In this instanc the catalyst concentration was approximately .8%. and approximately 2 parts by weight of catalyst solution per 100 of mixedgolens were used.. l l' As before, the solid polymer was passed from the kneader and eventually extruded through the plate of the extruder. In this instance also, a

- polymer of similar high tensile strength, high elongation and other-desirable characteristics was obtained.

By the device of this invention, there is thus provided a new polymerization mechanism by which the polymerization reaction is conducted in a sealed reactor from which the solid polymer is removed through an extruder which forms a solid seal of polymer to prevent the loss of gaseous or liquid portions of the reaction mixture; and the volatilized portions of the reaction mixture aire recovered in a closed system and separated into pure constituents for reuse and recycling.

While there are above disclosed but a limited number of embodiments of the invention, it is possible to produce still other embodiments without departing from the inventive concept herein disclosed.

The invention claimed is:

, 1. A polymerization process comprising the steps of mixing isobutylene with an inert liquefied normally gaseous organic refrigerant to bring it to a temperature within the range between C. and 165 C., subjecting the mixture to a kneading treatment, and polymerizing the mixture under the iniiuence of a kneading pulling and mixing action by ythe application thereto of a Friedel-Crafts type catalyst selected from' the group consisting of gaseous boron trifluoride, aluminum chloride dissolved in a solvent selected from the group consisting of methyl chloride, ethyl chloride, and carbon disuldde, and boron trifluoride dissolved in said inert refrigerant.

2. A polymerization process comprising the steps of mixing isobutylene with an inert liquefied normally gaseous organic refrigerant to bring it to a temperature within the range between 10 C. and 165 C., subjecting themixture to successive kneading treatments, polymerizing the mixture to produce a solid polymer under the influence of a kneading pulling and mixing action by the application thereto of a Friedel-Crafts 4 of a Friedel-Crafts type catalyst in iiuid condition comprising boron triuoride to produce a solid x polymer, and removing the solid polymer quickly from the pulling action by extruding the solid polymer. i

l5. A polymerization process comprising the steps of mixing isobutyiene with an inert liquefied normally gaseous hydrocarbon refrigerant to bring it to a temperature within the range between- 10 C. and 165 C.,-subjecting the mixture to successive kneading treatments, and polymerizing the mixture under the influence of the kneading pulling action by the application thereto of a Friedel-Crafts type catalyst Acomprising aluminum chloride dissolved in a solvent selected from the group consisting of methyl chloride, ethyl chloride, and carbon dlsulde.

6. A polymerization process comprising the steps of mixing isobutylene with an inert liqueed normally gaseous hydrocarbon refrigerant to bring it to a temperature within the range between 107 C. and 165 C., subjecting the mixture to successive kneading treatments, polymerizing the mixture to produce a solid polymer under the influence of the kneading pulling action by the application thereto of ,a Friedel-Crafts type catalyst comprising aluminum chloride dissolved in a solvent selected from the group consisting oi' methyl chloride. ethyl chloride, and carbon disulfide,y and removingthe solid polymer quickly f-rom the pulling action vby extruding the solid polymer.

7. A polymerization process comprising the steps of mixing together isobutylene and dimethyl butadiene at a temperature within the range between 50 C. and 165 C., polymerizing the mixture by the addition thereto of a Friedel- Crafts catalyst in uid condition comprising gaseous boron triiluoride while subjecting the lmixture to successive cold kneading treatments and during the polymerization reaction, removing the solid polymer quicklyfrom the polymerizer. l

type catalyst selected from the group consisting of gaseous boron trifluoride, aluminum chloride dissolved in a solvent selected from the group consisting of methyl chloride, ethyl chloride. and carbon disulde, and boron triuoride dissolved in said inert refrigerant, and removing -the solid polymer from the kneading pulling action.

3. A polymerization process comprising the steps of mixing isobutylenewith, an inert liqueed normally gaseous hydrocarbon refrigerant to bring it to a temperature within the range be,- tween 10 C. and 165` C., subjecting the mixture to successive kneading treatments, and polymerizing the mixture under the influence of the kneading pulling action -by the application thereto of a Friedel-Crafts type catalyst in fluid condition comprising boron triiiuoride.

' 4. A polymerization lprocess comprising the steps of mixing isobutylene with an inert liqueiled normally gaseous hydrocarbon refrigerant .to bring it to a temperature within the range between 10 C.rand 165 C., subjectingthe mixture to successive kneading treatments, polymerizing the mixture under the vinfluence of' the kneading pulling action by the application thereto 8. A polymerization process ycomprising the steps of mixing together isobutylene and dimethyl butadiene ata temperature within the range between 50 C. and 165 C., polymerizing the mixture by the addition thereto of a Friedel- Crafts catalyst in uid condition comprising dissolved boron triiluoride while subjecting the mixture to successive cold kneading treatments and during the-polymerization reaction. removing the solid polymer quickly from the polymerizer.

9. A polymerization process comprising the steps of mixing together isobutylene and dimethyl butadiene at a temperature within the range between 50 C. and 165 C., polymerizing the mixture by the addition thereto of a Friedel-l Crafts catalyst in iiuid condition, comprising aluminum chloride dissolved in a solvent selected from the group consisting of methyl chloride, ethyl chloride, and carbon disulfidewhile subjecting the mixture to successive cold kneading treatments andduring the polymerization reaction, removing the solid'polyzner quickly from the polymerizer.

10. A polymerization .process comprisingv the steps of mixing'together isobutylene and a conjugated dioleiln havingv 5 to 6 carbon atoms at a temperature within the range between 50 C. and C., polymerizing thezmixture by the addition theretol of a .Friedel-Crafts catalyst selected'from the group consisting of gaseous boron triuoride, aluminum chloridedissolved in a solvent selected from the group consisting of methyl chloride, ethyl chloride. and carbon disulfide, and boron triiluoride in solution in an inert liqueed normally gaseous organic refrigerant, subjecting the mixture to successive cold kneadfing treatments while Dlymerizing the mixture at said low temperature and during the polymerization reaction removing the polymer from the polymerlzer.

11. A polymerization process comprising the steps of mixing isobutylene and dimethyl butadiene in the presence of liquid ethylene et a temperature within the range between -50 C. and 165 C., polymerimng the mixture by the addition thereto of a. Friedel-Crafts catalyst in uid condition, comprising gaseous boron triiiuoride, gg 2,360,632

subjecting the mixture to successive cold kuend- 5 polymerizer.

MATTHEW D. MANN, Jl.

REFERENCES CITED l0 The following references are of record in the ille of this patent: A

. UNITED STATES PATENTS Name Date Number Y Mann et al. Oct. 17, 1944 

